Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/50—Phosphorus bound to carbon only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/136—Phenols containing halogens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/19—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/5399—Phosphorus bound to nitrogen

Definitions

• the present invention relates to curable vinylidene-fluoride copolymers having a high content in fluorine, the other comonomers deriving from fluorinated monomers with ethylene unsaturation.
• the present invention relates in particular to fluoroelastomeric copolymers based on vinylidene-fluoride (VDF), hexafluoropropene (HFP), optionally in the presence of one or more comonomers ethylenically unsaturated, the F amount being higher than 67% by weight.
• VDF vinylidene-fluoride
• HFP hexafluoropropene
• the invention relates to fluoroelastromeric copolymers based on VDF suitable to the preparation of fuel hoses and shaft seals.
• fluoroelastomeric polymers are required having good resistance to motor oils and/or to petrols containing polar substances, in particular alcohols.
• This property must be combined with good elastomeric properties such as compression set and good mechanical properties and good processability in molding both by compression by injection and by extrusion.
• copolymers can be also used for preparing O-rings used in the injectors coming into contact with petrols and/or oils containing polar substances.
• Object of the present invention are curable fluoroelastomeric compositions comprising
• the VDF ranges from 40 to 50 and HFP ranges from 50 to 60% by weight.
• the other comonomers are preferably from 0 to 30% of TFE and from 0 to 40% of perfuoroalkylvinylethers, preferably 0-20%;
• the onium compound used as accelerator in B) and C) and forming the adduct cation is generally selected from the following classes:
• R', R" and R 1 R 2 R 3 are alkylic, cycloalkylic, arylic, arylalkylic, oxyalkylic or polyoxyalkylic groups having a free or esterified terminal --OH function;
• R' and R" contain from 1 to 7 carbon atoms and can be linked each other so as to form an heterocyclic ring with the nitrogen atom while R 1 , R 2 , R 3 equal or different from each other contain from 1 to 18 carbon atoms;
• Q is selected from nitrogen, phosphorus, arsenic, antimonium
• R a , R b , R c , R d are selected from alkyls, aryls, alkylaryls or their combinations, two of said free radicals can be linked each other and the Q or S atom can form an heterocyclic ring.
• Preferred compounds are quaternary phosphonium compounds containing at least a phosphorus atom linked by four covalent simple bonds to four organic radicals, the organic radicals generally containing from 1 to 30 carbon atoms, preferably from 2 to 8.
• the organic radical being linear or branched, can contain heteroatoms.
• Preferred compounds are triphenylbenzylphosphonium, tetrabutylphosphonium.
• the accelerator can be also a blend of the compounds of the single classes I) to III), or of more compounds of the same class.
• the anion forming the adduct must be a curing agent and is generally selected from the polyhydroxy or polythiol compounds comprising the following classes:
• A is an arylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 14 carbon atoms, B is oxygen or sulphur and m is equal to 2 or 3;
• R 4a is an alkylene or cycloalkylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 18 carbon atoms and B is oxygen or sulphur; ##STR1## wherein R 2a is --SO--, --SO 2 --, --CO-- or a linear or branched alkylene radical containing from 1 to 9 carbon atoms and wherein the H atoms can be partially or wholly substituted with F atoms;
• R 3a is a perfluoropolyether or polyfluoroether chain, the average molecular weight by number Mn being from 360 to 2,000.
• the preferred cations are those deriving from aminophosphonium wherein the phosphorus atom is linked to a nitrogen atom and the other three covalent bonds are formed by organic radicals wherein the carbon is linked to phosphorus.
• the compound 1,1-diphenyl-1-benzyl -N-diethyl-phosphoramine is particularly preferred.
• Tetrabutyl phosphonium is particularly preferred.
• the bisphenol compounds (class X3) wherein the R 2a radical is the perfluoroalkyl group from 3 to 7 carbon atoms, and the OH are in para position, are preferred.
• the adduct can be prepared as follows.
• the polyhydroxy or polythiol compound is reacted, in aqueous solution or in a suitable solvent, for instance methanol, wherein the accelerator is soluble, in a first step, with a basic substance, for instance NaOH, KOH, Ca(OH) 2 and tBuO - K + , generally by using one equivalent gram of basic substance for mole of accelerator.
• a basic substance for instance NaOH, KOH, Ca(OH) 2 and tBuO - K +
• the reaction product is then reacted in a second step with an accelerator salt, for instance a chloride.
• the desired salt precipitates.
• the product is melted which through cooling, solidifies in flakes or pellets giving the adduct utilized in the present invention. This solid form is particularly suitable for its handling and its compounding in the blends.
• the polyhydroxy or polythiol compounds are used in molar ratios from 2:1 to 5:1 with respect to the accelerator.
• the curing blend comprises moreover, in order to obtain the cured products through heating,
• the basic compounds of point b) are usually selected from the group consisting of Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , metal salts of weak acids, such as for instance carbonates, benzoates, oxalates and phosphites of Ca, Sr, Ba, Na and K and mixtures of the aforesaid hydroxides with the abovesaid metal salts.
• composition according to the present invention commonly comprises other known components, such as fillers, for instance, carbon black, silica and dyes, generally from 5 to 30 phr; and processing adjuvants, for instance plasticizers, generally from 0.1 to 5 phr.
• fillers for instance, carbon black, silica and dyes
• processing adjuvants for instance plasticizers
• an advantage according to the present invention consists in that optimum results are obtained without using processing adjuvants, such as sulphones, which generally lead to a worsening of the final properties depending on the used accelerating system.
• the fluoroelastomeric copolymers are vinylidenefluoride copolymers with one or more fluorinated monomers having ethylene unsaturation.
• the copolymers of the present invention are VDF copolymers with hexafluoropropene.
• vinylethers PAVE
• PAVE per-fluoroalkylperfluorovinylethers, in particular perfluoromethylperfluorovinylether (MVE) and perfluoropropylperfluorovinylether.
• MVE perfluoromethylperfluorovinylether
• MVE perfluoropropylperfluorovinylether
• comonomers which can be utilized in amounts from 0 to 30% are for instance tetrafluoroethylene and/or chlorotrifluoroethylene.
• the olefinic monomers having up to 4° C. are for instance selected from ethylene and propene, the preferred being ethylene (Et), and are used in amounts from 0 to 25% by weight, preferably from 0 to 10%.
• copolymers of the invention combine a good chemical resistance with a high curing rate, essential requirement in transformation techniques such as injection molding.
• Such copolymers are capable of meeting more and more severe marketing specifications, which require good resistance to alcohols and to petrols containing alcohols especially methanol.
• VDF copolymers containing olefins particularly suitable due to their high resistance to alcohols and to bases, in particular oils containing amines, contain preferably the following monomer units:
• the fluoroelastomeric copolymers according to the present invention are prepared by emulsion polymerization according to well known techniques, preferably in the presence of radicalic initiators such as for instance persulphates, perphosphates, alkaline or ammonium perborates or percarbonates, optionally in combination with reducing agents such as sulphites, bisulphites, hyposulphites, phosphites, hypophosphites of alkaline or ammonium metals, or in combination with ferrous, cupreous or silver salts, or of other easily oxidable metals.
• radicalic initiators such as for instance persulphates, perphosphates, alkaline or ammonium perborates or percarbonates, optionally in combination with reducing agents such as sulphites, bisulphites, hyposulphites, phosphites, hypophosphites of alkaline or ammonium metals, or in combination with ferrous, cupreous or silver salts, or of other easily oxidable metals.
• Surfactants such as for instance ammonium perfluoro-octanoate or others known to be suitable in preparing fluoroelastomers can be present in the polymerization medium, for example ammonium perfluoro-octanoate.
• the fluoroelastomer is isolated from the polymeric latex by known methods, such as coagulation by addition of electrolytes or by cooling.
• the polymerization reaction is generally carried out at temperatures from 25° C. to 150° C., under pressure up to 10 MPa.
• the preparation of the elastomeric copolymers according to the invention can be carried out also by polymerization in the presence of a microemulsion formed by one or more perfluoropolyoxyalkylenes and water, according to the method described in European patent application No. 250767.
• the polymerization can be carried out also by using, instead of a microemulsion, an emulsion or a dispersion of perfluoropolyoxyalkylenes and water according to the method described in U.S. Pat. No. 4,789,717.
• the elastomeric composition For the curing of the polymers of the invention the elastomeric composition must be heated under pressure, at a temperature from 130° C. to 230° C., preferably from 160° C. to 200° C., for a period of time comprised from 0.5 to 60 minutes and, preferably, from 1 to 15 minutes.
• the obtained articles can then be post-cured in stove or in oven, at atmospheric pressure, at a temperature from 130° to 300° C., preferably from 200° C. to 275° C., for a period of time from 5 to 48 hours, and, preferably, from 10 to 24 hours.
• the accelerator has the following formula: ##STR4##
• the fluoroelastomer is TECNOFLON® TH 340 of Ausimont, vinylidene fluoride, hexafluoropropene and tetrafluoroethylene terpolymer having a Mooney viscosity ML (1+10) at 121° C. equal to 58, whose composition is:
• blends were cured at 170° C. in press and then to a post-curing in air stove between 200° C. and 250° C. for 24 hours.
• the curing evaluation was carried out by oscillating disc rheometer (ODR) of Monsanto type according to ASTM D 2084/81.
• Examples 1-3 were repeated using a fluoroelastomer TECNOFLON® T428E of Ausimont: terpolymer of vinylidenefluoride, hexafluoropropene and tetrafluoroethylene, having a Mooney ML (1+10) viscosity at 121° C. equal to 20, whose composition is:

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Rigid Pipes And Flexible Pipes (AREA)
• Sealing Material Composition (AREA)

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• 1994
  • 1994-05-27 IT ITMI941080A patent/IT1269845B/it active IP Right Grant
• 1995
  • 1995-05-24 RU RU95108224/04A patent/RU2152962C1/ru not_active IP Right Cessation
  • 1995-05-26 EP EP95108042A patent/EP0684277B1/de not_active Expired - Lifetime
  • 1995-05-26 DE DE69534957T patent/DE69534957T2/de not_active Expired - Lifetime
  • 1995-05-26 CA CA002150343A patent/CA2150343A1/en not_active Abandoned
  • 1995-05-26 AT AT95108042T patent/ATE324404T1/de not_active IP Right Cessation
  • 1995-05-26 US US08/451,160 patent/US5648430A/en not_active Expired - Lifetime
  • 1995-05-27 CN CN95108540A patent/CN1100821C/zh not_active Expired - Fee Related
  • 1995-05-29 JP JP13047895A patent/JP3979681B2/ja not_active Expired - Fee Related
• 1997
  • 1997-04-07 US US08/833,534 patent/US5830381A/en not_active Expired - Lifetime
• 2001
  • 2001-06-08 CN CNB011208937A patent/CN100369965C/zh not_active Expired - Fee Related

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